Isomerization of alpha phenylethyl phenols



:tacting, preferably-under heat, an'-'orthoor para- (alinha-phenYlthyl) ip'henol w'lth isulfuric =acid (concentrated sulfuric ==acid) 'th'ereby 'toconvert Patented May 11, 1948 IS OMEKIZRTION OF ALBHAAPHENYLETHYL liBHENOLS ,i-Kenneth B. -Goldblum, PittsfieldfMass "assignor to 'General -Electric I'Company, acorporati'on of JNewYork 'Nofbrawing. Application-Marcie21,-r194-5,

Serial No. 584,037

"7 Claims. '1

This invention relates tomew and useful improvements in .the art of treating --substituted phenols. fMore particularly the invention is concerned with the improved process which comprises contacting, with sulfuric acid, a mono- (alpha-phenylethyl) phenol :selectefd firom Lthe class consisting of -ortho-(alpha phenylethyl) phenol --and para-(alpha-phenylethyl) phenol thereby to :effect :conversion ofwa-teleastsomecfthe mono- (alpha phenylethyl) ,rphenolcfi-the: defined classzthat= is -beingrtreatedto: the other; member of the said-:class.

Alpha phenylethyl phenols are obtained, for example,= -by-condensing phenol withstyrenewhile admixed with a condensationcatalyst, ':e. :g.., 2a mineral-acid? suchpfor instance, as-Sulfuric acid, nitric acid, :hydrochloric ;.e,-cid,r,-phosphoric acid, etc.,and.isolating;thei alphaaphenylethyl phenols .iromthe reactionmass;ezgq by:distillation. :The

(omen-#619) processsince their useresultsma flecreased'yield products ofthe'reaction include,-. for:-example,

ing orthotor :para (alpha phenylethyl) phenol wherebythe one'maybe converted into the other. The starting substituted phenol maybe on'e that *hasxbeen iisolatediirom "the above describedi phe- 'n'olrstyrenezireaction-:mass or'oneithathas"been iotherwise ipro'duced.

iBriefly described, '1 my. method comprises conthe orthoor para-substituteid 'phenol"undergoing treatment to the corresponding para or ortho isomer. Although such catalysts as Friedel- Crafts-type catalysts, e. 1 g., .al-umir-ium chloride, boron trifluoride, etc.,- causesome: conversion -of the. starting orthoor para-(alpha-phenylet-hyl) :phenol .to w the 1 corresponding par-a or ortho isoof the converted product dueto'urrdesirable side reactions and "excessive "cracking-during the distillation process. Mineral acids, as a class, although "suitable for condensing phenol and styrene to yield-ortho-rand para (alpha phenylethyl) phenols, as wella's other'phenylethyl'phe- 'nols, "weret'found to be unsuitable-"in 1 converting ortho (alpha-phenylethyl) phenol or para alpha phenylethyl) phenol "to ithe corresponding para or ortho isomer. SuIfuric acid "alone was found to have the unique propertywof effecting the 'desire'dconversion. 'tsuchiacidsaaifor example,. hydrochloric, nitric-{phosphoric and trichloroacetic were ineffective.

' The addition ot'phen'ol to'the reaction'mixture of 'ortho- '-or para ;(-alpha=phenylethyl) .phenol and sulfuric acid increases "theyieid "of mono- (alpha-phenylethyl) phenols and, by reason. of the equilibrium Lrelation'ship hereinafter "discussed, directly increases the 5 yield of "converted 'substitutedphenol. "The amount'of added phenol, which apparentlyffunctions as a diluent, may be varied widelyifdepending, for example, upon the amount 'of' sulfuric acid used and 'the timefian'd .temperature'of reaction. ThusiI may employ, for

instance, .Dhenolin i'a'n amount corresponding to 'iromf'015v to 6 or more mols phenolfor each molof starting .or'tho- -.or para (-alphaephenylethyl) .phenol. (The added phenol is not essential.in.car-

rying my invention 'intoefie'ct. "However, its .use is advantageous. in! that itvretards. the formation of undesirableproducts ofithe reaction such for ,example, vas .ipolyphenyl phenols, poly- (alpha- .phenylethyl) phenols, tars,..etc.

Un'derioptimum. conditions .of; temperature, re-

actiontime. and catalyst concentration, the reaction masss.containseortho (alphar-phenylethyl) by distillation through-:a*packed= column. 'If the ortho and; para alpl'ia-"phenylethyl)- phenols are "first separated?- from the reaction 'mass as aisingle fraction containing-a mixture or these two. isomers thisfractionimay.be redistilled, ifldesired to separate the =one-isomerfrom the other. By repeating: the. conversion-treatment of theseparated *ortho or z para- (alphaephenylethyl) 3 phenol, --ex- .mer, such catalysts eareu-not .satisfactory; in my; pfillflnl?yieldeofithe';converted. substituted-p based on the original amount of unconverted sub-' .4 same, up to the point at which the conversion reaches an equilibrium. Any further increase in the period of reaction generally results in an increase in the amount of tarry matter and thus reduces the amount of converted substituted phenol in the reaction mass, although the ratio of ortho- (alpha-phenylethyl) phenol to para-(alphaphenylethyl) phenol in the said mass remains substantially the same.

Unless the sulfuric acid be neutralized, charring of the organic components of the mass may occur when distilling the mass to separate the distill- :able components including diluent phenol, if any, and converted and unconverted substituted phenols. Solid impurities or contaminants, for example the salt formed when the acid is neutralized, unreacted alkaline material, etc., preferably are removed, for instance by filtration, prior to the distillation step. I

My process for converting orthoor para- (alpha-phenylethyl) phenol to the corresponding para or ortho isomer may be carried out under a variety of temperature and pressure conditions, for example at normal (20 to 30 C.) or elevated temperature and at atmospheric, subatmospheric or superatmospheric pressure. Preferably the conversion is effected at a temperature within the range of 120 to 200 C. at atmospheric or substantially atmospheric pressure. Higher temperatures favor the formation of less desirable products, such as tars, etc.

The amount of sulfuric acid (concentrated sulfuric acid) may be varied over a wide range depending, for instance, upon the rapidity with which it is desired to effect the conversion. Generally, the amount of sulfuric acid will not exceed substantially 5 per cent by weight of the organic starting ingredient or ingredients. More particularly, th amount of concentrated sulfuric acid, e, g., acid containing about 90 to 96 per cent H2304, will not exceed substantially 5 per cent by weight of the starting orthoor para-(alphaphenylethyl) phenol or mixture of phenol and orthoor para-ialpha-phenylethyl) phenol, and may be considerably less, for example as little as about 0.2 per cent by weight thereof. Good results have been obtained in effecting the desired conversion using from about 0.5 to about 2.5 per cent by weight (of the other ingredient or ingredients) of concentrated sulfuric acid as a conversion catalyst. When the sulfuric acid is employed in an amount much above about 5 per cent by weight of the organic starting ingredient or ingredients, an objectionable amount of tarry material tends to be produced with a consequent decrease in the yield of converted isomer.

The time required for effecting the desired conversion likewise varies widely depending, for instance, upon the temperature at which the reaction is eifected and .the amount of sulfuric acid used. From a practical standpint it is desirable to continue the reaction until the reaction mass contains ortho-(alpha-phenylethyl) phenol and para- (alpha-phenylethyl) phenol in substantially an equilibrium ratio, more particularly the equilibrium ratio previously described. Ordinarily a satisfactory conversion will be effected in from about A to. or 12 hours. Under optimum conditions with regard to temperature and amount of sulfuric acid employed, I have found that a period of the order of 2 to 6 hours is most suitable. Increasing the time of reaction increases the yield of converted phenol, other conditions being the In order that those skilled in the art better may understand how my invention may be practiced, the following examples are given by way of illustration and not by way of limitation. The sulfuric acid was concentrated sulfuric acid (approximately 96% HZSOi, about 1.84 specific gravity). The ortho-(alpha-phenylethyl) phenol employed in certain of the examples boiled within the range of 300-302 C. at 742 mm. pressure. All parts and percentages are by Weight.

Example 1 Parts fig 01 Synthetic phenol 282. 3 3 Ortho-(alpha-phenylethyl) phenol 198.0 1 Concentrated sulfuric acid 3. 6

The above ingredients were mixed together in a three-necked, round-bottomed flask equipped with a reflux condenser, a mercury-sealed mechanical stirrer and a thermometer. The mixture was heated, with stirring, at a temperature of about 167. to 169 C, for approximately 8 hours. After cooling the reaction mass, it was neutralized with an excess of a concentrated aqueous solution of sodium carbonate. The mixture of sodium sulfate andunreacted sodium carbonate which In this example the same procedure and ingredients were used as in Example 1 with the exception that 6.4 instead of 3.6 parts sulfuric acid were employed. Also, the time of reaction was limited to 2 hours at 176-177 C. instead of 8 hours at 167169 C. Upon fractionally distilling the mass, 154 parts of a fraction containing orthoand para-(alpha-phenylethyl) phenols were obtained. Analysis of the fraction showed 58.7% para-substituted phenol and 41.3% orthosubstituted phenol. As in Example 1, so likewise in this example and in the examples that follow the isomers are separated from each other b fractional distillation.

Example 3 The same procedure and ingredients were used as in Example 2 with the exception that the temperature of reaction was 163-165 C. instead of 176-177 C. Fractional distillation yielded 163 parts of a mixture containing orthoand paraalphaephenylethyl) phenolszotfwliich 58.1% Mas: theapara isomer andid139Z%' theortho isomerz This exampleis the---sama as-.Examp1e-;31 with the exceptionthat; the period of; reaction; was..8= hours instead-of z'thours; Uponqfractional dis?- tillation of the reaction -massz there wasobtained; 161:5 parts of a mixture: which;.. upon showed that 58.5% was para- (alpha phenylethyll phenol and 41.5% was ortho- (alpha-phenylethyi)" phenol;-

Example 5 The same ingredients and procedure-wereused as in Example 1 with the-exception that 6i4in"- stead of 3.6 parts sulfuric a'cid wereemployed as catalyst and the reaction'was'conductedat ap proximately 145C. instead'0f167-169 C; 0n fractional distillation 16-2 partsof'a fraction containing 58.5% para-ialpha-phenyl'ethyl) phenol and 41.5% ortho (alpha-phenylethylT"phenol were obtained.

Similar yields wereobtainedwhen the amount of mineral acid conversion catalyst; specifically sulfuric acid; was increased"- to 12'parts; and'tlie' reaction time was'decreasedfrom 8 to' dhours'.

Example Approx. Mol

1 Ratio.

Synthetic phenol e. I 94.1. 1 Ortho-(alpha-phenylethyl) phenol" 198:0 l Concentrated sulfuric acid 4. 8

The above ingredients were-heated togetherffor 4: hours atv l87-i92 C. in a manner similar: to that described under Example 1. After neutralization, filtration of the neutralized mass to remove solid impurities and fractional distillation of the filtrate, I obtained about 146 parts of a fraction containing a mixture of orthoand para- (alpha-phenylethyl) phenols of which about 60% was the para isomer and 40% the ortho isomer.

An almost identical yield of paraand ortho- (alpha-phenylethyl) phenols was obtained when the mol ratio of phenol to ortho- (alpha-phenylethyl) phenol was raised from equimolecular proportions to 1.5 mols phenol per mol of the ortho isomer and the reaction temperature was lowered to 169l'76 C. while otherwise maintaining the same conditions. Further increases in the ratio of phenol to ortho-(alpha-phenylethyl) phenol re-.

sulted in a slight increase in the yield of the mixture of ortho and para isomers.

6; Examples-i Parts I i Synthetic.phe11o1 282.3 3 Piira-(alpha-piienylethyl) phenol 198.0 1 Concentrated-sulfuric acid; 6d

The above ingredients were heated togetherfon 4' hours at about 163'165C. in-a manner similar; to that-described under Example 1. Afterneu trali zation with a concentrated aqueous solution ot sodium carbonate'and'removal of the solid'im purities: e. g., salts resultingfrom the neutralization of the acid, etc.) by filtration, 158'partsofa fraction" containing orthoand para-(alphaphen-ylethyl) phenols were obtained upon fractional distill'atlon of the filtrate. Analysis ofthis fractionshowed that it oonsisted' of about 62%? para"- (alpha phenylethyl) phenol and38 ortho- (alpha-phenylethyl) phenoh The isomers are separated from-the fraction by distillation.

This example illustrates the-conversion ofortho-(alpha-phenylethyl) phenol to para- (alpha-phenylethyl) phenol in.the absenceof phenol as a diluent.

Parts Orthoalpha-phenylethyl) phenol 198:0 Concentrated'sulfuricacid 1.98

A. comparison of theyield- (96.6 parts) of 01113110 and-para?:(alpha-phenylethyl) phenols obtained inv this examplewiththe yields obtainedin Exeamples l t-o, 8,- inclusive, showsclearly the increased yields. of total= alphaephenylethyl pheno1s-:that--result.when phenol is a component of the initial reaction mixture. 6 Thus, in theprior.

examples wheredil-uent-phenol was presentin the reaction mass, thecombined yield of orthoand para-(alpha-phenylethyl) phenols ranged from about 74% to 83% of the amount of starting alpha-phenylethyl phenol whereas in this example the combined yield of orthoand para- (alpha-phenylethyl) phenols was only about 48.8% of the amount of starting ortho-(alphaphenylethyl) phenol.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. The process of producing para-(alphaphenylethyl) phenol which comprises heating a mixture containing phenol, ortho-(alpha-phenylethyl) phenol and concentrated sulfuric acid in an amount corresponding to, by weight, from about 0.2 to about 5 per cent of the total amount of phenol and ortho-(alpha-phenylethyl) phenol, said heating being continued until the reaction mass contains ortho-(alpha-phenylethyl) phenol said heating being continued at a temperature within the range of 120 to 200 C. until the reaction mass contains ortho-(alpha-phenylethyl) phenol and para-(alpha-phenylethyl) phenol in substantially an equilibrium ratio, neutralizing the acid reaction mass, filtering the neutralized mass to remove solid impurities, and distilling the filtrate to separate para-(alpha-phenylethyl) phenol.

3. The method of preparing para-(a1phaphenylethyl) phenol which comprises heating a mixture containing phenol and ortho-(alphaphenylethyl) phenol in an amount corresponding to from 0.5 to 6 mols of phenol per mol of ortho-(alpha-phenylethyl) phenol and, in addition to said phenols, concentrated sulfuric acid in an amount corresponding to, by Weight, from about 0.2 to about 5 per cent of the total amount of phenol and ortho-(alpha-phenylethyl) phenol, said heating being continued for a period ranging from about A to 12 hours thereby to obtain a reaction mass in which orthoand para- (alpha-phenylethyl) phenols are present in substantially an equilibrium ratio, neutralizing the acid reaction mass, filtering the neutralized mass to remove solid impurities, and separating para- (alpha-phenylethyl) phenol from the filtrate by distillation.

4. The process which comprises heating a mixture containing phenol, a mono-(alpha-phenylethyl) phenol selected from the class consisting of ortho-(alpha-phenylethyl) phenol and para- (alpha-phenylethyl) phenol, and concentrated sulfuric acid in an amount corresponding to, by weight, from about 0.2 to about 5 per cent of the total amount of phenol and mono-(alphaphenylethyl) phenol, said heating being continued until the reaction mass contains ortho- (alpha-phenylethyl) phenol and para-(alphaphenylethyl) phenol in substantially an equilibrium ratio, neutralizing the acid reaction mass, and distilling the neutralized mass to separate the orthoand para-(alpha-phenylethyl) phenols.

5. The process of producing ortho-(alphaphenylethyl) phenol which :comprises heating a mixture. containing phenol, para-(alpha-phenylethyl) phenol and concentrated sulfuric acid in an amount corresponding to, by weight, from about 0.2 to about 5 per cent of the total amount of phenol and para-(alpha-phenylethyl) Phenol, said heating being continued until the reaction mass contains ortho-(alpha-phenylethyl) phenol and para- (alpha-phenylethyl) phenol in substantially an equilibrium ratio, neutralizing the acid reaction mass, and distilling the neutralized mass to separate 'ortho-(alpha-phenylethyl) phenol.

6. The method of preparing ortho-(alphaphenylethyl) phenol which comprises heating a mixture containing phenol, para-(alpha-phenylethyl) phenol and concentrated sulfuric acid in an amount corresponding to, by weight, from about 0.2 to about 5 per cent of the total amount of phenol and para-(alpha-phenylethyl) phenol, said heating being continued at a temperature Within the range of to 200 C. until the reaction mass contains ortho-(alpha-phenylethyl) phenol and para-(alpha-phenylethyl) phenol in substantially an equilibrium ratio, neutralizing the acid reaction mass, filtering the neutralized mass to remove solid impurities, and distilling the filtrate to separate ortho-(alpha-phenylethyl) phenol.

7. The method of preparing ortho-(alphaphenylethyl) phenol which comprises heating a mixture containing phenol and para-(alphaphenylethyl) phenol in an amount corresponding to from 0.5 to 6 mols of phenol per mol of para- (alpha-phenylethyl) phenol and, in addition to said phenols, concentrated sulfuric acid in an amount corresponding to, by weight, from about 0.2 to about 5 per cent of the total amount of phenol and -para-(alpha-phenylethyl) phenol, said heating being continued for a period ranging from about to 12 hours thereby to obtain a reaction mass in which orthoand para- (alpha-phenylethyl) phenols are present in substantially an equilibrium ratio, neutralizing the acid reaction mass, filtering the neutralized mass to remove solid impurities, and separating ortho- (alpha-phenylethyl) phenol from the filtrate by distillation.

KENNETH B. GOLDBLUM.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED sTATEs PATENTS Number Name Date 2,189,805 Kyrides Feb. 13, 1940 2,315,556 Soday Apr. 6, 1943 2,329,671 Ward Sept. 14, 1943 

